Graft copolymers comprised of monomeric diacrylate esters of polyglycols on polyvinyllactams, acrylonitrile polymer compositions obtainable therewith, and method of preparation



Apr!1 10, 2 s. A. MURDOCK ETAL 3,029,

GRAFT COPOLYMERS COMPRISED OF MONOMERIC DIACRYLATE ESTERS OF POLYGLYCOLS ON POLYVINYLLACTAMS, ACRYLONITRILE POLYMER COMPOSITIONS OBTAINABLE THEREWITH, AND METHOD OF PREPARATION Filed Nov. 25, 1957 FILAMENTOUS ARTICLE COMPRISED OF AN ACRYLONITRILE POLYMER HAVING A GRAFT CO- POLYMER OF A MONOMERlC DIACRYLATE ESTER OF A POLYGLYCOL GRAFT COPOLYMERlZED UPON A VINYL LACTAM POLYMER INCORPORATED THEREIN.

IN V EN TORS I STANLEY A. MURDOCK ARDY ARMEN I BY Hiii Tg Arm/way;

United States Patent Ofiice 3,029,218 Patented Apr. 10, 1962 3,029,218 GRAFT COPGLYMERS CUMPRESEE) OF MGN O- MERIC DEIACRYLATE ESTER?) F PQLYGLY- C015 9N PGLYVINYLLACTAMS, ACRYLONH- TRILE POLYMER CQMPQdETIfiNS OBTAKNABLE THEREWITH, AND METHGD (PF PREPARATION Stanley A. Murdoch and Ardy Arman, Concard, Calitl, assignors to The Dow Chemical Company, Midland, Mich, a corporation of Deiavvare Filed Nov. 25, 1957, Ser. No. 698,769 31 Claims. (Cl. 260-455) The present invention resides in the general field of organic chemistry and contributes specifically to the polymer art, especially with respect to certain cross-linked, water-insoluble graft copolymer compositions and fiberforming polymer blends obtainable therewith. "It is particularly concerned with graft copolyrners of certain polyfunctional monomeric diacrylate and dimethacrylate esters of polyglycols upon polyvinyllactarn trunks or backbone substrates. Such graft copolymeric products have especial utility as dye-receptive, antistatic and stabilizing additaments for acrylonitrile polymer compositions which, advantageously, may be of the fiber-forming variety. The invention is thus also concerned with the compositions that may be obtained by blending the graft copolymers with acrylontirile polymers, as well as with shaped articles which have been fabricated from such compositons and which, as a consequence, have significantly enhanced properties and characteristics as regards improvements in and relating to enhanced dyereceptivity, minimized inherent propensity to accumulate electrostatic charges, natural stability to various deteriorating influences, including stability against becoming deleteriously influenced and degraded upon exposure to heat at elevated temperatures and to light. Within the scope and purview of the invention, there is comprehended (l) the various novel and utile graft copolymers of the indicated variety; (2) the advantageous polymer compositions, particularly fiber-forming compositions, obtained by blending the graft copolymers with acrylonitrile polymers; (3) various shaped articles fabricated from and comprised of the graft copolymer-containing acrylonitrile polymer compositions; and (4) methods for the preparation of the above indicated compositions.

It is the main purpose and primary design of the present invention to provide and make available graft copolymers of certain monomeric diacrylate and dimethacrylate esters of polyglycols upon vinyl lactam polymers that are especially well suited for being incorporated in acrylonitrile polymer compositions, particularly compositions of polyacrylonitrile, to serve in the indicated treble capacity of dye-assisting adjuvants, antistatic agents and stabilizing ingredients. It is also a principal aim and chief concern of the invention to provide and make available acrylonitrile polymer compositions and shaped articles therefrom that contain the above-indicated and hereinafter more fully delineated type of graft copolymeric additaments which compositions have, as intrinsic distinguishing characteristics, excellent receptivity of and acceptability for any of a wide variety of dyestuffs; permanently imbued antistatic properties that are unusually good for and not commonly encountered in polymeric materials of the synthetic, essentially hydrophobic varieties of such substances; and eflicacious natural stability to heat and light, as well as to certain chemical conditions, such as alkaline environments.

The graft copolymers of the present invention which have the indicated capacity and utility as additaments for acrylonitrile polymer compositions are comprised of (b) a polyvinyllactam trunk or base substrate upon or With which there is graft copolymerized a (a) diacrylate or dimethacrylate ester of certain polyglycols or their mixtures, as hereinafter more fully illustrated. Advantageously, in many instances, the graft copolymers of the present invention may be comprised of mixed graft substituents from diverse monomers, a portion of such graft substituents being derived from (1) the diacrylate of dimethacrylate esters of polyglycols and the remainder being graft copolymerized substituents on the polyvinyllactam substrate of (2) certain monomeric, vinyl or other alkenyl group-containing organic sulfonic acids or their derivatives which are hereinafter more fully delineated.

The polymer blend compositions of the present invention which fulfill the above-indicated ends and offer corollary advantages and benefits, particularly as fiberforming compositions as will hereinafter be manifest, are, in essence, comprised of an intimate and Practically inseparable blend or alloy constitution of (A) an acrylonitrile polymer that contains in the polymer molecule at least about percent by weight of polymerized acrylonitrile which, preferably, is of the fiber-forming variety and, most advantageously, is polyacrylonitrile and (B) a minor proportion of the above-indicated variety of beneficial graft copolymeric additament that functions in the described manner.

The methods of the invention by which the herein contemplated advantageous compositions may be made involve preparation of the graft copolymers, as well as incorporation of a minor proportion of the graft copolymer products as a beneficial additament in and with an acrylom'trile polymer base by any of several beneficial techniques, hereinafter more thoroughly defined, adapted to suitably accomplish the desired result.

Without being limited to or by the specific embodiments and modes of operation set forth, the invention is illustrated in and by the following didactic examples wherein, unless otherwise indicated, all parts and perccntages are to be taken on a weight basis.

EXAMPLE A Into a 500 ml., 3 neck, round bottom flask that was equipped with an efficient agitator, a nitrogen sparger and fractionating column, there was charged about grams of a polyglycol (having a molecular weight of about 600 and of the general structural formula:

134 grams of methyl methacrylate; 5 grams of paratoluene sulfonic acid; and about -6.7 grams of polymerization inhibiting hydroquinone. The mixture of charged ingredients in the reactor was brought to the boil and maintained at that temperature with the fractionating column set at total reflux until the overhead temperature reached about 64.5 C. When this temperature was attained, the overhead azeotrope of methanol and methyl methacrylate was removed for a period of about 6 hours at a temperature of 65 to 67 C. After this 6 hour period, the overhead temperature increased to about 80 C. and the reaction was terminated by removing the heat source. The excess methyl methacrylate was then removed from the reaction mass by vacuum distillation. About 1 liter of water was then added to the reaction mass and the solid polymer particles that had formed therein were removed by filtration. The aqueous solution of the polyglycol type monomer that remained was then passed through an ion exchange bed consisting of an anionic quaternary ammonium type resin (Dowex-l) to remove the hydroquinone. The uninhibited monomer solution was then stored at a temperature of about -29 C.

About 2.1 grams of the prepared monomeric diester was then charged to another reactor which was equipped with agitating means, a nitrogen sparger, and a total reflux condenser. There was also charged into the second reactor about 4.9 grams of polyvinylpyrrolidone (PVP) having a Fikentscher K-value of about 52; 28.3 grams of water and 0.04 grams of potassium persulfate. The resulting solution was heated to a temperature of about 50 C. and syntherrnally maintained thereat for a period of about 32 hours under a nitrogen blanket. The reaction was then terminated and the graft copolymer containing solution was removed from the reactor. The polymer product was a clear light brown solution that had a polymer content of about 19.5 percent. Upon analysis, it was found that about 95 percent of the diester monomer had been converted to a graft copolymer product with the PVP. The graft copolymer product containedabout 29 percent of the graft copolymerized substituents and 71 percent of the PVP.

The graft copolymer was found to be an excellent additive for enhancing the dye-receptivity of acrylonitrile polymer fibers to many of a wide variety of dyestuffs; decreasing the propensity of such fibers to accumulate charges of static electricity; and stabilizing the fiber to light, heat and alkaline media when it was incorporated polyacrylonitrile in the manner set forth in the following example.

EXAMPLE B Following the procedure of Example A, and using the "same monomeric diester of the polyglycol as therein described, a graft copoly'meric additament was prepared from the following charge:

. I l I Grams Monomeric diester tfro'm Example A) 29.3 Sodium styrene Sillfdfiait'e 8.2 (Fikentsche'r K-lialile Of 45) 87.5 Water 47 1.7 Ammonium persulfat'e 0.8

The charged ingredients which had a pH of about 6 (after adjustment with hydrochloric acid) were maintained at a temperature of about 70 C. for 21 hours. During this time the mixture of the diester monomer and the organic sulfonic acid monomer formed a mixed graft copolymer product on the PVP. Conversion of the 'monjorners to graft copolymer product was found to be about 91.3, percent. The graft copolymerproduct, which was obtained in the aqueous reaction mass as a slightly colored, water-insoluble :gel, was found to contain about 72 percent of PVP. about 2 3 percent of graft copolyrnerized diester units and about 5 percent of graft copo'lym'erized sodium styrene sulfonate units. A stable dispersion for use in impregnating polyacrylonitrile "aquagel fiber was made by putting the gel with additional water through a Waring Blendor so as to obtain an a'queoiisdispersionof 'the graft copolymer product con- 'taining about 9.4 percent of dispersed polymer solids.

olya crylonitrile fibers containing about 11.8 percent of the above copolymer product were prepared by impregnating filamentary structures that were in aquagel condition (after having been salt-spun and wet-stretched) :in and with a dissolved aqueous dispersion of the copolymerthat contained about 1.5 percent of the graft copoly- :ifrier'solids. The polyacrylonitrile aquagel fiber that was employed had been obtained by extruding a spinning solution of fiber-forming polyacrylonitrile comprised of about 1 0 partsof the polymer dissolved in 90 parts of a percent aqueous solution of zinc chloride through a spinnerette having 750 individual 6 mil diameter orifices into an aqueous coagulating bath that contained about 42 percent of dissolved zinc chloride to form a multiple filament tow. After being spun, the tow bundle of coagulated polyacrylonitrile aquagel fiber was washed substantially free from salt upon being withdrawn from the coagulating oath and then wet-stretched for orientation to a total stretched length that was about thirteen times its original extruded length. The aquagel fiber was then passed through the mentioned aqueous impregnating bath of the dissolved copolyrner additive so as to become impregnated therewith to the indicated extent.

Following the impregnation, the aquagel fiber was irreversibly dried at 150 C. to destroy the water-hydrated structure and convert it to a finished fiber form. It was then heat set for five minutes at 150 C. The finally obtained 2.5 denier fiber product had a tenacity of about 4.0 grams per denier, an elongation of about 27 percent, and a wet yield strength of about 0.96 grams per denier. The copolymer-containing acrylonitrile polymer fiber product was found to have excellent natural stability to heat and light as well as against becoming degraded under the influence of aqueous alkaline media at pH levels as high as 10. It was found to be nearly free of propensity to accumulate charges of static electricity upon handling; being about commensurate with viscose rayon fibers in this regard. As is widely appreciated, viscose rayon is not considered to be afflicted to a troublesome degree with problems due to static.

In addition, the graft copolymencontaining sample had good color and hand and was dyeable with all classes of dyestuffs as applied under normal dyeing conditions.

The fiber product dyed well to deep and level shades of coloration with Calcodur Pink 2BL, a direct type of dyestuff (Colour Index Direct Red 75, formerly Colour Index 353) and Sevron Brilliant Red 46, a basic dye formerly known as Basic Red 46 (Colour Index Basic Red 14).

The dyeing with Calcodur Pink ZBL was performed at the 4 percent level according to conventional procedure in which the fiber sample was maintained for about one hour at the boil in the dye bath which contained the dyestuif in an amount equal to about 4 percent of the weight of the fiber. The dye bath also contained sodium sulfate in an amount equal to about 15 percent of the weight of the fiber and had a bath-to-fiber weight ratio of about 30:1, respectively. After being dyed, the fiber was rinsed thoroughly with water and dried for about 20 minutes at C. The dye-receptivity of the Calcodur Pink ZBL-dyed fiber was then evaluated spectrophotometrically by measuring the amount of monochromatic light having a wave length of about 520 millimicrons from a standard source that was reflected from the dyed sample. A numerical value on an arbitrarily designated scale from zero to one hundred was thereby obtained. This value represented the relative comparison of the amount of light that was refiected from a standard white tile reflector that had a reflectance value of 316 by extrapolation from the. 0- scale. Lower reflectance values are an indication of better dye-receptivity in the fiber. For example, a reflectance value of 50 or less is fairly good. A value as low as about 20 to 25 for acrylonitrile polymer fibers dyed with 4 percent Calcodur Pink 2BL is generally considered by those skilled in the art to be representative of a degree of dye-receptivity that readily meets or exceeds the most rigorous practical requirements and is ordinarily assured of receiving general commercial acceptance and approval. The 4 percent Calcodur Pink 2BL reflectance value of the copolymer-containing fiber product was about 18.

The antistatic properties of the graft copolymer-containing fiber were then determined by' measuring the electrical conductance of the fiber product at various humiditiesv As is also appreciated by those who are skilled in the art, the basis for such a test is that all fibers have a tendency to generate static electricity upon being handled. Only those that are possessed of sufficient electrical conductance to dissipate the charge as quickly as it forms are not hampered by the bothersome effects of static electricity. Thus, a measure of the electrical conductance of a fiber is a good indication of its ability to dissipate static electricity. The conductivities of the various fiber samples tested were found by determining their electrical resistances. Resistance, of course, is the reciprocal quantity of conductivity. In order to permit various fiber samples to be compared on a common basis, the conductivities of the samples tested were actually measured as volume resistivities according to the following formula:

Volume Resistivity (Resistance) (cross-sectional area) Path length between electrodes to which sample being tested is attached The units of volume resistivity are ohm-cmP/cm.

Prior to being tested, the graft copolymer-containing polyacrylonitrile fiber prepared in the indicated manner was vat dyed in the conventional manner with Cibanone Green BF Dbl. Paste (Colour Index Vat Green No. 1). A portion of the vat dyed sample was then subjected to five (5) consecutive No. 3-A accelerated wash tests in accordance with the American Association of Textile Chemists and Colorists (AATCC) Manual. The actual resistivity of the merely vat dyed sample as well as that of the sample that had been both vat dyed and washed were then determined (after the samples being tested were conditioned for seventy-two hours at the particular temperature and relative humidity conditions involved in each of the tests) by tautly connecting a web-like sample of the yarn between two electrodes, each of which were 9 centimeters long spaced parallel 13 centimeters apart, and across which there was applied a 900 volt direct current potential. For purposes of comparison, the volume resistivities of cotton, wool and an unmodilied polyacrylonitrile fiber (obtained in the same way as the copolymer-containing fiber but without having the graft copolymeric additament incorporated therein) were also tested in the indicated manner along with the graft copolymer-containing fiber in accordance with the present invention.

The results are set forth in the following tabulation which indicates the volume resistivities obtained at various relative humidities (RH) at 23 C. of each of the samples tested.

Table 1.VOZume Resistivities of Various Fiber Samples Compared to Polyacrylonitrile Fibers impregnated With Graft Copolymer of Sodium Styrene Sulfonute on PVP As is apparent in the foregoing, the graft copolymercontaining samples, even after being vat dyed and dyed and severely washed, had electrical conductance properties much superior to ordinary polyacrylonitrile and only slightly poorer than cotton. At the same time, the physical properties of the copolymer-containing fibers were excellent, being about equal to those of the unmodified polyacrylonitrile fiber.

EXAMPLE C Following the procedure of Example A and using the 6 same monomeric diester as therein describe, a graft copolymer product was prepared from the following charge:

Monomeric diester from Example A "grams" 1.1 PVP (Fikentscher K-value of 57) do.. 2.6 Water ml 19.0 Potassium persulfate grams 0.02

The pH of the reaction mass was adjusted to about 9.5 with sodium hydroxide. The graft copolymerization was carried out for 16 hours at 50 C. A colorless, waterinsoluble graft copolymer product was obtained that could be easily dispersed in water in order to form aqueous dispersions suitable for impregnation of acrylonitrile polymer fibers in accordance with the technique set forth in Example B. About 84.3 percent of the monomeric diester was found to have been converted to graft copolymer product. The product graft copolymer was found to contain about 74 percent of PVP and about 26 percent of graft copolymerized diester substituen'ts. When the graft copolymer product was incorporated in polyacrylonitrile fibers in the manner set forth in the second example, it was found to be an excellent dye-assisting additive and permanent antistatic agent for the fibers. The graft copolymer-containing fibers had good dye-receptivity, excellently low static characteristics and excellent physical properties.

EXAMPLE D Polyglycol having average molecular weight of about 6000 and of the structural formula:

HO-(CH CH O) CH CH OH grams..- 1000 Methyl methacrylatc do 200 Para-toluene sulfonic acid do 20 Hydroquinone do 10 The charged ingredients in the reactor were heated to a temperature of about 120 C. The fractionating column on the apparatus was operated at total reflux until the overhead temperature came to about 65 C. After this, distillate was removed from the column at 6568 C. for a 4 hour period. The excess methyl methacrylate was then removed under vacuum (2 mm. Hg absolute) for 2 hours. One liter of water was then added to the monotrier-containing reaction mass and the polymeric solids filtered out. The resulting aqueous monomer solution was then passed through a bed of Dowex 1 ion exchange resin to remove the hydroquinone polymerization inhibitor. The uninhibited aqueous monomer solution was then stored at about 30 C. until ready for use.

About 37.4 grams of the monomeric dimethacrylate ester of the polyglycol was then mixed with about 87.0 grams of PVP having a Fikentscher K-value of about 45; 499 grams of water; and 0.4 grams of azobisisobutyronitrile. The charge, having a pH of about 6; was graft copolymerized in the manner set forth in the preceding examples over a 24 hour period at 50 C. under nitrogen. At the end of this period, more than 50 percent of the monomer had been converted to a graft copolymer prodnot which was water insoluble, but which could be easily dispersed in water by simple mechanical means. The graft copolymer product was found to contain about 18 percent of the graft copolymerized dimethacrylate polyglycol diester units and about 82 percent of PVP. It was found to be an excellent dye additive and permanent antistatic agent for acrylonitrile polymer fibers when it was incorporated in them in the manner set forth in the second example. The graft copolymer-containing fibers had good dye-receptivity, excellent static characteristics, satisfactory stability and suitable physical properties.

EXAMPLE E The general procedure of Example D was employed to prepare. a mixed graft copolymer from the following charge which was polymerized under nitrogen for about 18 hours at a temperature of 50 C.:

Conversion of the monomers to graft copolymer product was found to be about 90 percent. The graft copolymer product was found to contain about27 percent of graft copolymerized polyglycol diester units; about 1 percent of graft copolymerized sodium styrene sulfonate units; and about 82 percent of PVP. As in the foregoing examples, the graft copolymer product Was found to be an excellent dye-assisting additive, stabilizer and permanent anti-static agent for acrylonitrile polymer fibers When it was incorporated in them according to the manner set forth in the second example. The graft copolymer-containing fibers had very, good acceptance of any of a wide variety of dyestuffs, extremely low static characteristics and sutiable stability and physical properties.

Excellent results may also be obtained when the foregoing is repeated to prepare graft copolymer additives from poly-N-vinylcaprolactam, poly-N-vinyl-5-methyl-2- pyrroiidone, poly-N-vinylpiperidone and other vinyl lactam polymers or with any other ofthe moonmeric substances Within the scope .of the invention. Results similar to those set forth in the foregoing can likewise be obtained when the graft copolymer additaments are incorporated in polyacrylonitrile and other acrylonitrile polymer fibers to provide articles in accordance with the present invention by blending the graft copolymer and the fibercontaining acrylonitrile polymer in a. spinning composition or dope prior to its-extrusion into filamentary products by either Wet spinning or dryspinning techniques. In such instances, incidentally, it may be desirable, in order to secure optimum benefit in the practice of the invention, to employ relatively larger quantities of the graft copolymeric additament than when surface impregnation is performed so that the presence of effective quantities of the additarnent at or near the peripheral portion of the article is assured.

The monomeric diacrylate and dimethacrylate esters of polyglycols that are employed for the preparation of the graft copolyrnersinthe practice of the present invention are, as is indicated in the foregoing, prepared from the. esterification of polyethylene or polypropylene glycols, mixtures of such polyglycols, or mixed polyethylenepolypropylene polyglycols ,with acrylic or methacrylic acids, respectively, or methyl or ethyl esters or other reactive derivatives of such acids. The polyglycols that are employed for the preparation of the difunctional monomeric diesters must be double-ended, i.e., have active hydroxyl groups at both ends and not the monoether or similar .polyglyco ls which have other non-reactive terminal substitutions. Advantageously, the polyglycols that are employed for the preparation. of the monomers have molecular Weights from about 300 to 9,000, preferably between .about 600 and 1200. The monomeric diesters utilized in the practice of the present invention may be represented by the generic formula:

wherein Z and G are independently selected from the group consisting of hydrogen and alkyl radicals contain.- ingfrom 1 to about 2 carbon atoms (advantageously being hydrogen or methyl); m is a number having an averagevalue from 6 .to 100; and n is a number having an average value from 0 to about 10,. with the limitation that the value of n is less than about half the value oi m.

If desired, as has been indicated and demonstrated, the monomeric diesters used in the present invention may be, employed in, combination. or mixture with other varieties of monomers in order to prepare mixed graft copolymers having specific properties and effects; particularly with respect to their capability for accepting greator numbers of diverse types of dyestuffs. For example, the monomeric diacrylate and dimethacrylate esters of the polyglycols generally provide graft copolymers showing excellent acceptance of acid or direct types of dyestuffs. However, other varieties of monomers, such as those which may provide acidic chemical characteristics in the resulting graft copolymer structure, may frequentiy be used with great advantage to enhance the dye-attracting potency of the resulting graft copolymeric additive to basic dyestuffs. Thus, it may frequently be an advantage to graft copolymerize mixtures of the monomeric diesters with monomeric, vinyl or other alkenyl group-containing, organic sulfonic acids or derivatives thereof that are selected from the group of such compounds (includingmixtures thereof) consisting of those represented by the formulae:

(Aromatic organic sulfonic acid compounds) OHz=CH-(CHZ)WSOQX (Ill) (Alkenyl organic sulfonlc acid compounds) CH7:C'COO(CI'I2)!1?SO3X d (IV) (Sulfoalkylacrylate organic sulfonic acid compounds) CHa=C-CONH(CH2) 11"SO3X (Acrylol taurine homolog compounds) and 011 -(3-0 H ,NI-I- (6H2) r-S 0 X' (Allyl taurino homolog compounds) all wherein X is hydrogen, an aliphatic hydrocarbon radical containingrfrom l to 4 carbon atoms or an alkali metal ion (including sodium, potassium and lithium); Y is hydrogen, chlorine or bromine; R is methyl or ethyl; Z is hydrogen or methyl; m has a numerical value in whole number increments from 0 to 2; n has a numerical value of 1 or 2; p is O or 1; and r has a numerical value of l to 4.

Besides those specifically illustrated herein, other organic sulfonic acids may also be utilized inrnixture'with" the monomeric po'lyglycol diesters for preparation of the water-insoluble graftcopolymeric additarnents that may advantageously be employed in the practice of the present invention include such organic sulfonic acids as 2-propene sulfonic acid; sodium para-vinylbenzene sulfonate; 2- and/ or 3-sulfopropyl acrylate; ot-sulfoacrylic acid; sodium vinyl toluene sulfonate; potassium ortho-chlorostyrene sulfonate; 2-hydroxy-3-sulfopropyl acrylate, sodium salt; sodium 3-allyloxy-2-hydroxypropane sulfonate; 4-sulfophenyl acrylate, sodium salt; and N-ailyl-iminodi-(Z- ethane sulfonic acid). Still others, grouped according to their general structural designations, are setforth in the following representative, but by no means exhaustive, list:

AROMATIC ALKENYL 'GROUP CONTAINING SULFONIC' ACID COMPOUNDS (FORMULA II) Para-styrene sulfonic acid. Ortho-styrene sulfonic acid Para-isopropenyl benzene sulionic acid Para vinyl benzyl sulfonic acid Ortho-isopropenyl benzyl sulfonic acid Sodium para-styrene sulfonate' Potassium ortho-styrene sulfonate Methyl para-styrene sulfonate Ethyl para-vinyl. benzyl sulfonate Ortho-vinylbenzene sulfonic acid Isopropyl ortho-isopropenyl benzene sulfonate n-Butyl ortho-styrene suifonate Tertiary butyl para-styrene sulfonate 2-chloro-4-vinyl benzene sulfonic acid 4-bromo-2-isopropenyl benzene sulfonic acid 3-vinyl toleue -sulfonic acid, sodium salt 2-ethyl-4-vinyl-benzene sulfonic acid 2,3-dichioro-4-vinyl benzene sulfonic acid 2,3,5-tribromo-4-vinyl benzene sulfonic acid 2-chloro-3-vinyl-toluene-6-suifonic acid 2,3-diethyl-4-vinyl-benzyl sulfonate, sodium salt ALKENYL SULFONIC ACID COMPOUNDS (FORMULA III) Ethylene sulfonic acid Sodium ethylene sulfonate Potassium ethylene sulfonate Methyl ethylene sulfonate Isopropyl ethylene sulfonate l-propene 3-sulfenic acid l-propene l-sulfonic acid, sodium salt l-propene 2-sulfonic acid, ethyl ester l-butylene 4-sulfcnic acid, n-butyl ester l-butylene 3-sulfonic acid Tertiary butylene sulfonic acid SULFOALKYLACRYLATE COMPOUNDS (FORMULA IV) Sulfomethylacrylate Z-sulfoethylacrylate sulfomethylmethacrylate, sodium salt Z-mlfoethylmethacryiate, methyl ester 2-sulfoethylmethacrylate, potassium salt ACRYLOYL TAURINE AND HOMOLOGOUS COMPOUNDS (FORMULA V) N-acryloyl taurine N-acryloyl taurine, sodium salt N-methacryloyl taurine, methyl ester N-methacryloyl taurine, potassium salt N-acryloyl taurine, ethyl ester N-acryloyl-aminomethane sulfonic acid N-methacryloyhaminomethane sulfonic acid, sodium salt Methyl N-rnethacryloyl-aminomethaue sulfonate ALLYL TAURINE AVD HOMOLOGOUS COMPOUNDS (FORMULA VI) Allyl taurine Allyl taurine, sodium salt Allyl taurine, potassium salt Methallyl taurine Methallyl taurine, methyl ester Methallyl taurine, isopropyl ester N-allyl-aminomethane sulfonic acid Sodium N-allyl-aminomethane sulfonate Lithium N-methallyl-aminomethane sulfonate n-Butyl N-allyl aminomethane sulfonate The vinyl lactam polymers that are utilized in the preparation of the graft copolymeric additaments of the present invention may be any of those (or their mixtures) which are variously characterized and generically known to the art as poly-N-vinyl lactams of poly-l-vinyl lactarns. Such polymers as have been described or which may be prepared from the mentioned varieties of monomers that are involved in US. Patents Nos. 2,265,450; 2,371,804; and 2,335,454 may be suitably employed in the practice of the invention. Advantageously, although not in a limiting sense, the poly-N-vinyl lactarn that is used for the manufacture of the graft copolymer may be one having a molecular weight between about 3.8)(10 and 2.8 1O as evidenced by a Fikentscher K-value between about 25 and 55. Beneficially, as has been indicated, the poly-N-vinyl lactams that are employed are poly-N-vinylpyrrolidone or poly-N-vinylcaproiactam, particularly the former.

The graft copolymers of the present invention may generally be prepared by methods of polymerization, such as those which have been demonstrated in the foregoing illustrative exampies, that employ such polymerization catalysts as persulfates, organic and inorganic peroxide and azo type materials in quantities that are conventional for such uses. The graft copolymers may oftentimes be prepared by polymerizing the monomeric constituent onto the vinyl lactam polymer under the influence of actinic radiations, such as ultraviolet light, or high energy irradiation such as by means of X-rays, electron beams, emissions from radioactive sourcesand the like, or simply by heating or evaporating the monomer and polymer-containing polymerization mixture. The graft copolymers may be prepared in both aqueous and organic solvent vehicles using temperatures for the desired polymerization that may vary from about room, temperature to the boiling point of the polymerization mixture. It is ordinarily satisfactory to conduct the reaction at a temperature of about 50 to or 100 C. Usually, depending on the specific factors that may be involved, the graft copolymerization may be accomplished satisfactorily within a time period of about 5 to 60 hours.

The compositions of the graft copolymer can vary Within rather wide limits. The content of the monomeric polyglycol diester constituent that is graft copolymerized on the vinyllactam polymer may advantageously be between about 20 and 80 percent by weight of the resulting graft copolymer product and, more advantageously, between about 30 and 50 percent by weight. In many cases, especially to secure optimum dye-receptivity, near equivalent or about commensurate or equal Weight proportions of the vinyl lactarn polymer and the monomeric diester constituent graft copolymerized thereto may be employed with benefit in the graft copolymeric additaments. When mixtures of the monomeric diesters with monomeric organic sulfonic acids are employed to prepare mixed graft copolymer products on the vinyl lactam polymer, it is desirabie for the total quantity of graft copolymerized constituents on the vinyllactam polymer to remain within be above stated ranges (i.e., from 20 or 30 to 50 or 80 weight percent) with from about 10 to mole percent of the graft copolymerized substituents being comprised of graft copolymerized monomeric polyglycol diester units and, more advantageously, from 30 to 60 mole percent of the graft copolymerized constituents consisting of polymerized monomeric polyglycol diester units With the ba1- ance being polymerized monomeric organic sulfonic acid units upon the 80 to 20 percent by weight of the vinyl lactam polymer that is contained in the graft copolymer structure.

The graft copolymers upon PVP and other vinyl 1actam polymers of the polyglycol diacrylate or dimethacrylate monomers are wax-like solids whose properties depend to some extent on the molecular weight of the precursor polyglycols from which the monomeric diesters are derived. All of the graft copolymer products are cross-linked, water-insoluble materials which, as mentioned and illustrated, may be dispersed readily in water or organic solvents.

The polymerization system that is employed for the preparation of the graft copolymers used in the present invention may consist of as much as 50 percent by Weight of the monomers to be polymerized in the aqueous or other medium. The amount of polymerizable constituents that are provided in the copolymerization system may be influenced somewhat by the manner in which it is intended to incorporate the product in the synthetic polymer compositions in order to provide the compositions of the invention.

If, for example, it is intended to incorporate the graft copoiymer products by blending into a fiber-forming composition prior to its fabrication into shaped articles, the graft copolymerization system may, if desired, contain about equal proportions by weight of the charged polymerizable constituents and the polymerization medium which, preferably, is miscible with and tolerable in the spinning solution solvent being used. In such cases, the graft polymer product may ordinarily be obtained as an easilydispersed gel that, after being dried and isolated from unreacted monomer, may readily be directly incorporated in the fiber-forming composition.

If the incorporation of the graft copolymeric additament in a fiber-forming composition is to be achieved by impregnation therewith of an already-formed shaped article of the composition, it may be desirable to effect the-polymerization so asto directly form the polymerization system as a suitable applicating emulsion or suspension of the graft copolymeric product. For such purposes, the polymerization system may be prepared to contain as little as 2 or 10 percent by weight of the polymerizable monomeric and polymeric ingredients. Preferably, such a polymerization may be conducted under the influence of vigorous agitation to facilitate preparation of an emulsified or thoroughly dispersed product. It may also be beneficial under such circumstances (although'it is usually not necessary) to incorporate a dispersant or emulsifying agent in the polymerization system to facilitate obtaining a stable and homogeneous emulsified product. Such a method for preparing the graft copolymeric additaments that are employed in the present invention may be especially appropriate when they areintended to be applied to acrylonitrile polymer fibers and the like that are derived from aquagels in the course of their manufacture, such as the acrylonitrile polymer fibers that are wet spun from aqueous saline solutions of the fiber forming polymer.

In such instance as has been demonstrated, the emulsified, water-insoluble, graft copolymeric additaments may be impregnated into the fiber while it is in a swollen or gel condition, as an acrylonitrile polymer fiber in an aquagel condition, in order to obtain the desired copolymer-containing product.-

In this connection, when it is desired to blend the graft copolymeric additament in a synthetic polymer fiber-forming solution prior to its extrusion, such as an aqueous saline acrylonitrile polymer solution, the water-insoluble graft copolymer may be physically reduced by commiuution to a sufiiciently fine state to permit its dispersion in spinnablecondition throughout the blended spinning solution in the event that it is otherwise insoluble in the solvent. While this may be accomplished by diverse techniques, it is generally advantageous to comminute the graft copolymer in the presence of the non-dissolving solvent, such as an aqueous saline polyacrylonitrile solvent, to form a stable suspension that may be more conveniently blended with the spinning solution of the synthetic polymer, such as an aqueous, saline acrylonitrile polymer spinning solution. Thus, if the aqueous saline polyacrylonitrile'solvent that is being employed is an aqueous solution of zinc chloride or its equivalent that contains at least about 55 percent and preferably about 60 percent by weight of dissolved zinc chloride, it may be advantageous to comminute the graft copolymeric additament while it is in a mixture with the saline solvent solution that contains between about 5 and percent by weight of the ccpolymer. Analogous procedures may be employed when other solvents are involved. Ball or rod mills or other attrition apparatus may be employed satisfactorily for the comminution. It is generally beneficial under such circumstances to avoid the use of balls or rods that are made of metal since they may contaminate the product, especially when aqueous saline solvents are utilized. Porcelain or other ceramic parts may usually be employed with advantage. A stable suspension of the graft copolymeric additament in the acrylonitrile polymer solvent that is suitable for blending in the spinning solution of the acrylonitrile polymer to provide a spinnable composition may usually be obtained bymilling the mixture of graft copolymeric additament and solvent for an extended period that may exceed hours. The suspension that is thereby obtained may then be directly blended in the proper proportions with the acrylonitrile polymer spinning solution to provide a composition in accordance with the present invention.

If desired, the copolymer-containing acrylonitrile polymer compositions may comprise as much as 20 or more percent by weight of the graft copolymeric additament, based on the weight of the composition. Usually, however, suitable properties and characteristics and better fiber-forming properties in a given composition may be achieved when lesser proportions of the copolymeric additament are imcorporated therein. An appreciable improvement in dye-receptivit antistatic properties and stability may frequently be obtained when a quantity of the copolymeric additarnent that is as small as 3 (and even as low as l or less) percent by weight is employed. Advantageously, an amount between about 3 and 15 percent by weight of the copolymeric additament may thus be utilized in the composition. Greater advantages may often accrue when the amount of the copolymeric additament that is incorporated in the composition is in the neighborhood of 616 percent by Weight, based on the Weight of the composition.

As has been indicated, the graft copolymeric additaments may be incorporated in the acrylonitrile polymer compositions according to various techniques. Thus, for example, the copolymeric additament and the acrylonitrile polymer may be directly blended in order to provide the composition which, incidentally, may be used for any desired fabrication purpose in addition to fiber-forming and the like. Beneficially, the polymers may be comminuted, either separately or in combination, before being intimately blended together by mechanical or other means. The blended polymers may be prepared into suitable fiber-forming systems by dissolving or otherwise dispersing them in a suitable liquid medium. Or, the

compositions may be provided in fiber-forming system by sequentially dispersing the polymers in any desired order in a suitable medium, as by incorporating the graft copolymeric additament in a prepared acrylonitrile polymer spinning solution, dope or the like.

As is evident from the illustrative examples heretofore included, a highly advantageous technique for providing the compositions, particularly when acrylonitrile polymer fiber products are involved, is to apply or impregnate the copolymeric additament from an aqueous dispersion thereof to a shaped acrylonitrile polymer article that is in an aquagel condition in a manner similar and analogous to that employed for the impregnation of vinyl lactarn polymers as described in the disclosure contained in the copending application of George W. Stanton, Theodore B. Letferdink, Richard W. Meikle and Mary J. Charlesworth for a Method and Composition for Rendering Polyacrylonitrile Readily Dyeable having Serial No. 333,385 which was filed on January 26, 1953, now abandoned. Thus, an acrylonitrile polymer filamentary article that has been spun from an aqueous saline spinning'solution may be conveniently passed, after its coagulation and while it is in an aquagel condition, through a water bath containing the dissolved graft copolymen'c additament in order to impregnate the filament with the graft copolymer and provide a composition and an article in accordance with the invention. In addition, it is oftentimes possible for in situ polymerization techniques to be accomplished and relied upon to provide the graft copolymeric additament in the acrylonitrile polymers in either fabricated or unfabricated form.

The compositions of the invention may advantageously be utilized in or with fiber-forming systems of any desired type in order to provide fibers and the like according to procedures and techniques that are conventionally employed for such purposes in the preparation of fibers and such' related shaped articles as filaments, strands, yarns, tows, threads, cords and other funicular structures,

ribbons, tapes, films, foils, sheets and the like which may be manufactured from synthetic polymeric materials. It is frequently desirable to employ concentrated solutions of salts of mixtures of salts as the dispersing or dissolving media for such purposes. Such solutions may, as has been indicated, contain at least about 55 percent by weight, based on the weight of the solution, of zinc chloride or other known saline solvents for the polymer. Acrylonitrile polymer fiber products that are spun from saline fiber-forming systems may, by way of further illustration, be coagulated in more dilute saline solutions of a like or similar nature and may then be processed after coagulating according to conventional techniques of washing, stretching, drying, finishing and the like with the modifn cation of the present invention being accomplished prior or subsequent to the spinning as may be desired and suitable in particular instances.

The acrylonitrile polymer fiber products in accordance with the present invention (one of which is schematically illustrated in the sole figure of the accompanying drawing) have excellent physical properties and other desirable characteristics for a textile material and have a high capacity for and are readily and satisfactorily dyeable to deep and level shades with any of a wide variety of dyestuffs. For example, they may be easily and successfully dyed according to conventional procedures using acid, vat, acetate, direct, naphthol and sulfur dyes.

Such dyestulfs, by way of didactic illustration, as Calcocid Alizarine Violet (Colour Index 61710, formerly Colour Index 1080), Sulfanthrene Red 313 (Colour Index Vat Violet 2), Amacel Scarlet GB (Colour Index 11110) and Direct Red 1also known as Amacel Scarlet BS, (and having American Prototype Number 244), Calcodur Pink 2BL (Colour Index 253, also more recently, Colour Index Direct Red 75), Naphthol ASMX (Colour Index 35527), Fast Red TRN Salt (Colour Index Azoic Diazo Component l1), and Immedial Bordeaux G (Colour Index Sulfur Brown 12) may advantageously be employed for such purposes.

Other dyestuffs, by way of further illustration, that may be utilized beneficially on the graft copolymer-containing, polymer blended fiber products of the invention include such direct cotton dyes as Chlorantine Fast Green 5BLL (Colour Index Direct Green 27), Chlorantine Fast Red 7B (Colour Index Direct Red 81), Pontamine Green GX Conc. 125 percent (Colour Index Direct Green 6), Calcomine Black EXN Conc. (Colour Index Direct Black 38), Niagara Blue NR (Colour Index Direct Blue 151) and Erie Fast Scarlet 4BA (Colour Index Direct Red 24); such acid dyes as Anthraquinone Green GN (Colour Index Acid Green 25), Sulfonine Brown 2R (Colour Index Acid Orange 51), Sulfonine Yellow 26 (Colour Index Acid Yellow 40), Xylene Milling Black 2B (Colour Index Acid Black 26A), Xylene Milling Blue FF (Colour Index Acid Blue 61), Xylene Fast Rubine 3GP PAT (Colour Index Acid Red 57), Calcocid Navy Blue R Conc. (Colour Index Acid Blue 120), Calcocid Fast Blue BL (Colour Index Fast Blue 59), Calcocid Milling Red RR (Colour Index Acid Red 151), Alizarine Levelling Blue 2R (Colour Index Acid Blue 51), Amacid Azo Yellow G Extra (Colour Index Acid Yellow 63); such mordant-acid dyes as Alizarine Light Green GS (Colour Index Acid Green 25); such basic dyes as Brilliant Green Crystals (Colour Index Basic Green 1) and Rhodamine B Extra S (Colour Index Vat Blue 35); such vat dyestuffs as Midland Vat Blue R Powder (Colour Index Vat Blue 35), Sulfanthrene Brown G Paste (Colour Index Vat Brown 5), Sulfanthrene Blue 2B Dbl. paste (Colour Index Vat Blue 5), and Sulfanthrene Red 313 paste (Colour Index Vat Violet 2); various soluble vat lyestufis; such acetate dyes as Celliton Fast Brown BRA Extra CF (Colour Index Dispersed Red 13), Artisil Direct Red 38F and Celanthrene Red 3BN Conc. (Both Colour Index Dispersed Red 15), Celanthrene Pure Blue 14 Acetamine Yellow N (Colour Index Dispersed Yellow 32; B-Naphthol 2-chloro-4-nitroaniline, an azoic dye;

such as sulfur dyes as Katigen Brilliant Blue GGS High Conc. (Colour Index Sulf. Blue 9) and Indo Carbon CLGS (Colour Index Sulf. Blue 6); and various premetallized dyestuffs.

The dyed products are generally light fast and stable to heat and are well imbued with a good resistance of crocking. In addition, the dyed products exhibit good washfastness and retain the dye-assisting, static-reducing and stabilizing graft copolymeric additament in a substantially permanent manner, despite repeated exposure and subjection to washing, laundering and dry cleaning treatments.

What is claimed is:

l. Graft copolymer comprising between about 26 and percent by weight of (a) a polyfunctional diester of a polyglycol having the formula:

wherein Z and G are independently selected from the group consisting of hydrogen and alkyl radicals containing from 1 to 2 carbon atoms; In is a number having an average value from 6 to 100; and n is a number having an average value from 0 to 10; with the limitation that the value of n is less than about half of the value of m; and (b) from 80 to 20 percent by weight of a vinyl lactam polymer.

2. The graft copolymer of claim 1, containing in the polymer molecule between about 30 and 50 percent by Weight of said diester graft copolymerized with the vinyl lactam polymer.

3. The graft copolymer of claim 1, wherein said vinyl lactam polymer with which said diester is graft copolymerized is poly-N-vinylpyrrolidone.

4. Graft copolymer comprising between about 20 and 80 percent by weight of (a) a mixture of monomers consisting of from about 10 to mole percent of a (l) diester of a polyglycol of the formula: CH =CZ-CO--(OC H (OC I-I OOCGC=CH (I) wherein Z and G are independently selected from the group consisting of hydrogen and alkyl radicals containing from 1 to 2 carbon atoms; in is a number having an average value from 6 to and n is a number having an average value from 0 to 10; with the limitation that the value of n is less than about half of the value of m; and (2) from about 90 to 10 mole percent of at least one alkenyl group-containing organic sulfonic acid compound selected from the group consisting of those represented by the formulae:

all wherein X is selected from the group consisting of hydrogen, saturated aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and bromine; R is selected from the group consisting of methyl and ethyl; Z is selected from the group consisting of hydrogen and methyl, m is an integer from BRS 400 percent (Colour Index Dispersed Blue 1) and 75 0 to 2; n is an integer from 1 to 2; p is an integer from to 1; and r is an integer from 1 to 4; and (b) from about 80 to 20 percent by weight of a vinyl laotam polymer.

5. The graft copolymer of claim 4 containing in the Fwd.

' polymer molecule between about 30 and 50 percent by wherein Z and G are independently selected from the group consisting of hydrogen and alkyl radicals containing from i to 2 carbon atoms; m is a number having an average value from 6 to 100; and n is a number having an average value from 0 to '10; with the limitation thatthe value of n is less than about half of the value p of m; wi-th between about 80 and 20 percent by weight of a vinyl lactam polymer. 7

8. Method for the preparation of a graft copolymer which comprises polymerizing between about 21 and 80 percent by weight based on the weight of the resulting graft copolymer of (a) a. mixture of monomers consisting of from about 10 to 99 mole percent of (1) a diester of a polyglycol of the formula:

CH =CZ--CO(OC H (0C H wherein Z and G are independently selected from the group consisting of hydrogen and alkyl radicals containing'from' 1 to 2 carbon atoms; In is a number having an average value from 6 to 100; and n is a number having an average value from G to 10; with the limitation that the value of n is less than about half of the value of m; and (2) from about 90 to 10 mole percent of at least one alkenyl group-containing organic sulfonic acid compound selected from the group consisting of those having the formulae:

all wherein X is selected from the group consisting of hydrogen, saturated aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and bromine; R is selected from the group consisting of methyl and ethyl; Z is selected from the group con sisting of hydrogen and methyl, m is an integer from 0 to 2; n is an integer from 1 to 2; p is an integer from 0 to 1; and r is an integer from 1 to 4; with (b) between about 80 and percent by weight of a vinyl lactam polymer.

9. Composition comprising a major proportion of (A) a fiber forming polymer of ethylenically unsaturated monomeric material containing at least about 80 percent by weight of acrylonitrile and (B) a minor proportion of up to about 20 percentfoy weight, based on the weight it"; i. of the composition, of a graft copolymer of (a) between about20 and weight percent of a diester of a polyglycol having the formula:

wherein Z, and G are independently selected from the group consistingv of hydrogen and alkyl radicals con taining from 1 to 2 carbon atoms; m is anumber having an average value from 6 to 100;. and n is a number have ing an average value from 0. to 10;.withthelirnitation that the value of n is less than labouthalf ofthe value of m; and (b) from about 80 to 20 weight percent of a vinyl lactam polymer.

10. The composition of claim 9 containing between about 6 and 10 percent by weight, based on the weight of the composition, of said graft copolymer. l

11. The composition of. claim 9, wherein said graft copolymer contains between about 30 and 50 percent by weight of said monomer graft copolymerized with said vinyl lactam polymer.

12. The composition. of claim 9, wherein component (B) is a graft copolymer of a monomer of Formula I wherein mis 12 and n is 0 and G and Z are both methyl grafted with poly-N-vinyl pyrrolidone.

13. The composition of claim 9, wherein component:

(B) is a graft copolymer of a monomer of Formula I wherein mis 15 and n is 3 and G and Z are both methyl grafted with poly-N-vinyl pyrrolidonen 1 14. The composition of claim9, wherein the acrylonitrile polymer is polyacrylonit rile. 1 A v t i 15. The composition of claim 9, dispersed in a solvent for polyacrylonitrile.

16. A filamentary shaped article'andcomprised of a composition that is set forth in'claim 9. l

17. Composition comprising a major proportion of (A) a fiber forming polymerof an ethylenically unsaturated monomeric material containing at least about 80 percent by weight of acrylonitrile and (B) a minor proportion of up to about 20 percent by weight, based on the weight of the composition, of a graft copolymer of(a) between about 20 and 8 weight percent of a mixture of monomers consisting of (1) from about 10 to mole percent of a diester of a polyglycol of the formula:

whereinZ and G are independently selected .from tthe. group consisting of hydrogen andalkyl radicals contain-. ing from 1 to 2 carbon atoms; m is a number havingaanr average value from 6 to and n is a number having an average value from 0 to 10; with theliniitation that the value of n is less than about half of the value of m; and. (2) from about. 9.0 to 10 mole percent of at leastone monomeric alkenyl group-containing organic sulfonic acid compound .selectedfrom the group consisting of those having the formulae:

all wherein X is selected from the group consisting of 7 hydrogen, saturated aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and bromine; R is selected from the group consisting of methyl and ethyl; Z is selected from the group consisting of hydrogen and methyl, m is an integer from to 2; n is an integer from 1 to 2; p is an integer from 0 to 1; and r is an integer from 1 to 4; and (b) from about 80 to 20 weight percent of a vinyl lactam polymer.

18. The composition of claim 17 containing between about 6 and 10 percent by weight, based on the weight of the composition, of said graft copolymer.

19. The composition of claim 17, wherein said graft copolymer contains between about 30 and 50 percent by Weight of said mixture of monomers graft copolymerized with said vinyl lactam polymer.

20. The composition of claim 17, wherein said mixture of monomers comprises from about 30 to 60 mole percent of said diester of a polyglycol of the Formula I.

21. The composition of claim 17, wherein component (B) is a graft copolymer of a mixture of a monomer of Formula I wherein m is 12 and n is 0 and G and Z are both methyl with sodium styrene sulfonate grafted with poly-N-vinyl-pyrrolidone.

22. The composition of claim 17, wherein component (B) is a graft copolymer of a mixture of a monomer of Formula I wherein m is 12 and n is 0 and G and Z are both methyl with 2-sulfoethylmethacrylate, sodium salt grafted with poly-N-vinylpyrrolidone.

23. The composition of claim 17, wherein component (B) is a graft copolymer of a mixture of a monomer of Formula I wherein m is 15 and n is 3 and G and Z are both methyl with vinylbenzyl sulfonate, sodium salt grafted with poly-N-vinylpyrrolidone.

24. The composition of claim 17, wherein the acrylonitrile polymer is polyacrylonitrile.

25. The composition of claim 17, dispersed in a solvent for polyacrylonitrile.

26. A filamentary shaped article comprised of a composition that is set forth in claim 17.

27. Method for the preparation of a dye-receptive, antistatic, stable to light and heat, synthetic, linear, hydrophobic polymer composition which comprises immersing an aquagel of a fiber forming polymer of an ethylenically unsaturated monomeric material containing at least about 80 percent by weight of acrylonitrile in the form of a shaped article into a dispersion of a graft copolymer of (a) between about and 80 Weight percent of a monomeric diester of a polyglycol of the formula:

wherein Z and G are independently selected from the group consisting of hydrogen and alkyl radicals containing from 1 to 2 carbon atoms; in is a number having an average value from 6 to 100; and n is a number having an average value from 0 to 10; with the limitation that the value of n is less than about half of the valume of m; and (b) from about 80 to 20 Weight percent of a vinyl lactam polymer, until between about 3 and 20 percent by weight of said graft copolymer, based on the weight of the resulting dry composition weight, is incorporated in said aquagel; and drying said graft copolymer-containing aquagel to convert it from the aquagel condition to a finished shaped article form.

28. The method of claim 27, wherein said acrylonitrile polymer is polyacrylonitrile.

29. Method for the preparation of a dye-receptive, antistatic, stable to light and heat, synthetic, linear, hydrophobic polymer composition which comprises immersing an aquagel of a fiber forming polymer of an ethylenically unsaturated monomeric material containing at least about 80 percent by weight of acrylonitrile in the form of a shaped article into a dispersion of a graft copolymer of (a) between about 20 and 80 weight percent 18 or" a mixture of monomers consisting of (1) from about 10 to mole percent of a monomeric diester of a polyglycol of the formula:

CH ==CZ-CO(OC H (OC H OOC--GC=CH (I) wherein Z and G are independently selected from the group consisting of hydrogen and alkyl radicals containing from 1 to 2 carbon atoms; m is a number havin an average value from 6 to and n is a number having an average value from 0 to 10; with the limitation that the value of n is less than about half of the value of m; and (2) from about 90 to 10 mole percent of at least one monomeric alkenyl group-containing organic ulfonic acid compound selected from the group consisting of those having the formulae:

Y, Rm

0132 (CHfir-SMX OH OH--(CHa)mSO5X (III) OHFU-OO O-(GH2) n-SO K i av) OH2=CCONH-(CH;|)H-SOSX CHFC-GHPNH (OHQ)K-SOBX Z (VI) all wherein X is selected from the group consisting of hydrogen, saturated aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and bromine; R is selected from the group consisting of methyl and ethyl; Z is selected from. the group consisting of hydrogen and methyl, m is an integer from 0 to 2; n is an integer 1 to 2; p is an integer from 0 to 1; and r is an integer from 1 to 4; and (b) from about 80 to 20 weight percent of a vinyl lactam polymer, until between about 3 and 20 percent by weight of said graft copolymer, based on the weight of the resulting dry composition Weight, is incorporated in said aquagel; and drying said graft copolymer-containing aquagel to convert it from the aquagel condition to a finished shaped article form.

30. The method of claim 29, wherein said graft c0- polymer contains between about 30 and 50 percent by weight of said mixture of monomers graft copolymerized with said vinyl lactam polymer and wherein said monomer mixture contains from about 30 to 60 mole percent of said monomeric diesterof a polyglyc-ol of the Formula i.

31. The method of claim 29, wherein said acrylonitrile polymer is polyacrylonitrile.

References Cited in the title of this patent UNITED STATES PATENTS 2,417,312 MacGregor Mar. 11, 1947 2,418,696 Cameron et al Apr. 8, 1947 2,614,289 Cresswell et al Oct. 21, 1952 2,643,990 Ham June 30, 1953 2,735,831 Coover Feb. 21, 1956 2,776,270 Coover et al. Jan. 1, 1957 2,776,271 Coover et al Jan. 1, 1957 2,790,783 Coover Apr. 30, 1957 2,821,519 Glickrnan Jan. 28, 1958 2,837,496 Vandenberg June 3,1958

7 FOREIGN PATENTS 715,194 Great Britain Sept. 8, 1954 

17. COMPOSITION COMPRISING A MAJOR PROPORTION OF (A) A FIBER FORMING POLYMER OF AN ETHYLENICALLY UNSATURATED MONOMERIC MATERIAL CONTAINING AT LEAST ABOUT 80 PERCENT BY WEIGHT OF ACRYLONITRILE AND (B) A MINOR PROPORTION OF UP TO ABOUT 20 PERCENT BY WEIGHT, BASED ON THE WEIGHT OF THE COMPOSITION, OF A GRAFT COPLYMER OF (A) BETWEEN ABOUT 20 AND 80 WEIGHT PERCENT OF A MIXTURE OF MONOMERS CONSISTING OF (1) FROM ABOUT 10 TO 90 MOLE PERCENT OF A DIESTER OF A PLYGLYCOL OF THE FORMULA: 